5-epi-Asperlin | 57378-87-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 5-epi-Asperlin
• 英文别名: [(2R,3R)-2-[(2S,3R)-3-methyloxiran-2-yl]-6-oxo-2,3-dihydropyran-3-yl] acetate
• CAS: 57378-87-7
• 化学式: C₁₀H₁₂O₅
• 分子量: 212.202
• InChiKey: SPKNARKFCOPTSY-MCOJJJQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-epi-Asperlin 在 Alcaligenesis sp. lipase PL 作用下， 以 异丙醚 、 水 为溶剂， 反应 5.0h， 以50%的产率得到(5R,6R,1'S,2'R)-5,6-dihydro-5-hydroxy-6-(1',2'-epoxypropyl)-2H-pyran-2-one
  参考文献：
  名称：

  Total synthesis of (+)-asperlin

  摘要：

  Syntheses of (+)-asperlin 1 were achieved via two different synthetic routes. 1,2-Addition of alpha-furyl anion to (2R,3S)-2-'butyldimethylsilyloxy-3-chlorobutanal 6 gave (1S,2R,3S)-1-(2-furyl)-2-'butyldimethylsilyloxy-3-chlorobutanol 7, which was converted to the chiral intermediate, (1S,2R,3R)-1-(2-furyl)-2,3-epoxybutanol 8 (37% overall yield from 6) for the synthesis of (+)-1. The second synthesis of (+)-asperlin 1 from (2R,3S)-6 was achieved in 8% overall yield, based on a combination of the indium-assisted stereoselective addition of 3-bromopropenyl acetate 9 to (2R,3S)-6 and the ring closing metathesis (RCM) using Grubbs catalyst. (C) 2008 Elsevier Ltd. All riehts reserved.

  DOI：

  10.1016/j.tetasy.2008.04.011
• 作为产物：
  描述：

  (+/-)-(E)-1-(2-furyl)but-2-en-1-ol 在 吡啶 、 chromium(VI) oxide 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 calcium hydride 、 bis(acetylacetonate)oxovanadium 、 silica gel 、 三乙酰氧基硼氢化钠 、 D-(-)-酒石酸二异丙酯 、 溶剂黄146 作用下， 以 二氯甲烷 、 溶剂黄146 、 异丙醇 为溶剂， 反应 20.25h， 生成 5-epi-Asperlin
  参考文献：
  名称：

  Yang, Zhi-Cai; Jiang, Xiao-Bin; Wang, Zhi-Min, Journal of the Chemical Society. Perkin transactions I, 1997, # 3, p. 317 - 321

  摘要：

  DOI：

文献信息

• Stereocontrolled Synthesis of (±)-Asperlin and Related Stereoisomers Using Organotitanium Reagent
  作者：Hiroaki Hiraoka、Kyoji Furuta、Nobuo Ikeda、Hisashi Yamamoto

  DOI：10.1246/bcsj.57.2777

  日期：1984.10

  The naturally occurring antibiotics asperlin and related fungal metabolites containing a 5,6-dihydro-2-pyrone moiety have been synthesized stereoselectively. The propargyltitanium reagent derived from 1-trimethylsilyl-3-(tetrahydropyranyloxy)propyne condensed with crotonaldehyde affords the corresponding erythro alcohol as the major product, which is converted to (±)-asperlin and the related three stereoisomers in seven steps.

  天然存在的抗生素曲林及其含有5,6-二氢-2-吡喘部分的类似真菌代谢物已被立体选择性地合成。由1-三甲基硅基-3-（四氢吡喃氧基）丙炔衍生的炔基钛试剂与巴豆醛缩合，主要产物为赤型醇，经过七步反应转化为（±）-曲林及其相关的三个立体异构体。
• Syntheses of natural (+)-phomalactone, (+)-acetylphomalactone (+)-asperlin and their isomers.
  作者：Tetsuya MURAYAMA、Takeyoshi SUGIYAMA、Kyohei YAMASHITA

  DOI：10.1271/bbb1961.51.2055

  日期：——

  (+)-Phomalactone, (+)-acetylphomalactone, (+)-asperlin and their isomers were synthesized from 3-triethylsiloxypropyne and (S, E)-1-formyl-2-butenyl benzoate, which was easily prepared from (2R, 3S, E)-1, 2-cyclohexylidenedioxy-4-hexene-3-ol.

  (+)-Phomalactone, (+)-acetylphomalactone, (+)-asperlin 及其异构体由 3-三乙基硅氧丙炔和(S, E)-1-甲酰基-2-丁烯基苯甲酸酯合成，后者很容易由 (2R,3S,E)-1,2-环己基亚二氧基-4-己烯-3-醇制备。
• Peculiar Sharpless kinetic resolution of 2-furylmethanol and its application to the synthesis of (+)-Asperlin
  作者：Zhi-Cai Yang、Wei-Shan Zhou

  DOI：10.1016/0040-4039(95)01170-m

  日期：1995.7

  A peculiar kinetic resolution of E-1-(2-furyl)-2-buten-1-ol (1), which produced two oxidation products, pyranone (2) and epoxyalcohol (3), was developed by using the modified Sharpless reagents. A short synthesis of (+)-Asperlin was achieved starting from the optically active resolution products.

  利用改进的Sharpless试剂，开发了产生两种氧化产物吡喃酮（2）和环氧醇（3）的特殊的E-1-（2-呋喃基）-2-buten-1-ol（1）动力学拆分剂。 。从旋光拆分产物开始，短合成了（+）-Asperlin。
• MURAYAMA, TETSUYA;SUGIYAMA, TAKEYOSHI;YAMASHITA, KYOHEI, ARG. AND BIOL. CHEM., 51,(1987) N 8, 2055-2060
  作者：MURAYAMA, TETSUYA、SUGIYAMA, TAKEYOSHI、YAMASHITA, KYOHEI

  DOI：——

  日期：——
• Total synthesis of (+)-asperlin
  作者：Hideaki Akaike、Hidekazu Horie、Keisuke Kato、Hiroyuki Akita

  DOI：10.1016/j.tetasy.2008.04.011

  日期：2008.5

  Syntheses of (+)-asperlin 1 were achieved via two different synthetic routes. 1,2-Addition of alpha-furyl anion to (2R,3S)-2-'butyldimethylsilyloxy-3-chlorobutanal 6 gave (1S,2R,3S)-1-(2-furyl)-2-'butyldimethylsilyloxy-3-chlorobutanol 7, which was converted to the chiral intermediate, (1S,2R,3R)-1-(2-furyl)-2,3-epoxybutanol 8 (37% overall yield from 6) for the synthesis of (+)-1. The second synthesis of (+)-asperlin 1 from (2R,3S)-6 was achieved in 8% overall yield, based on a combination of the indium-assisted stereoselective addition of 3-bromopropenyl acetate 9 to (2R,3S)-6 and the ring closing metathesis (RCM) using Grubbs catalyst. (C) 2008 Elsevier Ltd. All riehts reserved.